Bottom Line:
However, the surface-insensitive RCR reaction leads to more dense monolayers and, therefore, to much better chemical stability, with lasting protection of the Si surface against oxidation.This is reflected in longer minority carrier lifetimes, lower reverse currents in the dark, and improved photovoltaic performance, over what is obtained if only one of the mechanisms operates.It further suggests an approach for effective passivation of other semiconductors.

ABSTRACTWe report on the passivation properties of molecularly modified, oxide-free Si(111) surfaces. The reaction of 1-alcohol with the H-passivated Si(111) surface can follow two possible paths, nucleophilic substitution (SN) and radical chain reaction (RCR), depending on adsorption conditions. Moderate heating leads to the SN reaction, whereas with UV irradiation RCR dominates, with SN as a secondary path. We show that the site-sensitive SN reaction leads to better electrical passivation, as indicated by smaller surface band bending and a longer lifetime of minority carriers. However, the surface-insensitive RCR reaction leads to more dense monolayers and, therefore, to much better chemical stability, with lasting protection of the Si surface against oxidation. Thus, our study reveals an inherent dissonance between electrical and chemical passivation. Alkoxy monolayers, formed under UV irradiation, benefit, though, from both chemical and electronic passivation because under these conditions both SN and RCR occur. This is reflected in longer minority carrier lifetimes, lower reverse currents in the dark, and improved photovoltaic performance, over what is obtained if only one of the mechanisms operates. These results show how chemical kinetics and reaction paths impact electronic properties at the device level. It further suggests an approach for effective passivation of other semiconductors.

Mentions:
nucleophilic substitution(SN) of an alkoxide (conjugated base of the alcohol) thatproceeds (for the ideal Si(111) surface) through a pentavalent siliconcomplex as an intermediate species21,26 (Figure 1a);

Mentions:
nucleophilic substitution(SN) of an alkoxide (conjugated base of the alcohol) thatproceeds (for the ideal Si(111) surface) through a pentavalent siliconcomplex as an intermediate species21,26 (Figure 1a);

Bottom Line:
However, the surface-insensitive RCR reaction leads to more dense monolayers and, therefore, to much better chemical stability, with lasting protection of the Si surface against oxidation.This is reflected in longer minority carrier lifetimes, lower reverse currents in the dark, and improved photovoltaic performance, over what is obtained if only one of the mechanisms operates.It further suggests an approach for effective passivation of other semiconductors.

ABSTRACTWe report on the passivation properties of molecularly modified, oxide-free Si(111) surfaces. The reaction of 1-alcohol with the H-passivated Si(111) surface can follow two possible paths, nucleophilic substitution (SN) and radical chain reaction (RCR), depending on adsorption conditions. Moderate heating leads to the SN reaction, whereas with UV irradiation RCR dominates, with SN as a secondary path. We show that the site-sensitive SN reaction leads to better electrical passivation, as indicated by smaller surface band bending and a longer lifetime of minority carriers. However, the surface-insensitive RCR reaction leads to more dense monolayers and, therefore, to much better chemical stability, with lasting protection of the Si surface against oxidation. Thus, our study reveals an inherent dissonance between electrical and chemical passivation. Alkoxy monolayers, formed under UV irradiation, benefit, though, from both chemical and electronic passivation because under these conditions both SN and RCR occur. This is reflected in longer minority carrier lifetimes, lower reverse currents in the dark, and improved photovoltaic performance, over what is obtained if only one of the mechanisms operates. These results show how chemical kinetics and reaction paths impact electronic properties at the device level. It further suggests an approach for effective passivation of other semiconductors.